Electroplating processes are widely employed in industrial environments for a large variety of metallic coatings, ranging from technological to decorative applications. Even if the galvanic electrodeposition is certainly a mature technology, new concepts, novel applications, environmental legislation and the new material requirements for next-generation devices make the scientific research in this field still very active. This review focuses mostly at the decorative and wearable applications, and aims to create a bridge between the past knowledge and the future direction that this process, i.e., electrodeposition, is taking. Both the theoretical fundamentals as well as some of the most widespread practical applications—limited to metallic and alloy coatings—are explored. As an integral part of the industrial process, we take a look at the main techniques thought which the quality control of deposits and surfaces is carried out. Finally, global industrial performance and research directions towards sustainable solutions are highlighted.

Electrochemical deposition methods are increasingly being applied to advanced technology applications, such as microelectronics and, most recently, to energy conversion. Due to the ever growing need for device miniaturization and enhanced performance, vastly improved control of the growth process is required, which in turn necessitates a better understanding of the fundamental phenomena involved. This overview describes the current status of and latest advances in electrodeposition science and technology. Electrochemical growth phenomena are discussed at the macroscopic and atomistic scale, while particular attention is devoted to alloy and compound formation, as well as surface-limited processes. Throughout, the contribution of Professor Foresti and her group to the understanding of electrochemical interfaces and electrodeposition, is highlighted.

We investigate the influence of chloride <mml:math display="inline"><mml:msup><mml:mi mathvariant="normal">Cl</mml:mi><mml:mo>−</mml:mo></mml:msup></mml:math>Cl− ions in a broad range of chloride concentrations on the kinetics and mechanism of copper electrodeposition from sulfate-based acidic electrolytes. Chloride ions influence copper deposition through two competitive effects: at low <mml:math display="inline"><mml:msup><mml:mi mathvariant="normal">Cl</mml:mi><mml:mo>−</mml:mo></mml:msup></mml:math>Cl− concentration (few mM), chloride ions depolarize the Cu reduction process, while higher <mml:math display="inline"><mml:msup><mml:mi mathvariant="normal">Cl</mml:mi><mml:mo>−</mml:mo></mml:msup></mml:math>Cl− concentrations induce complexation of copper species and cause a cathodic polarization of the deposition process. Cu reduction proceeds through two parallel mechanisms, a direct two-step reduction and a chloride-mediated route, whose relative importance depends on the amount of chloride present. A transition between these two mechanisms can be identified both by steady-state and impedance methods; however, the chloride concentration at which it occurs depends on the time scale probed by the two techniques. Impedance measurements further demonstrate that the presence of chlorides changes the double-layer structure.

We study electrical properties and breakdown phenomena in metal/aluminum oxide/metal and electrolyte/aluminum oxide/metal contacts, with the aim to achieve a better understanding of failure modes and improve the performance of model electrowetting systems. Electrical conduction in anodic aluminum oxide dielectrics is dominated by the presence of electrically active trapping sites, resulting in various conduction mechanisms being dominant within distinct voltage ranges until hard breakdown occurs. Breakdown voltage depends on its polarity, due to the formation of a p-i-n junction within the oxide; such asymmetric behavior tends to disappear at larger oxide thickness. Electrolyte/dielectric contacts present an even more pronounced asymmetry in breakdown characteristics: a cathodic bias results in breakdown at low voltage, while under anodic bias high field ionic conduction starts before breakdown occurs. These phenomena are interpreted in terms of electrochemical reactions occurring at the surface: cathodic processes contribute to oxide dissolution and failure, while anodic processes result in additional oxide growth before breakdown.